Bis(tri(dimethylamino)silyl)ethane



Patented Oct. 20, 1970 3,535,357 BIS[TRI(DIMETHYLAMINO)SILYL]ETHANE Charles E. Creamer, North Tonawanda, N.Y., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Original application Feb. 24, 1966, Ser. No. 529,665, now Patent No. 3,451,964. Divided and this application Mar. 3, 1969, Ser. No. 803,931

Int. Cl. C07f 7/02 US. Cl. 260-4482 1 Claim ABSTRACT OF THE DISCLOSURE A bis [tri(dimethylamino) silyl]ethane compound useful as an ingredient in curable aminosilicon compositions.

This application is a division of application Ser. No. 529,665, filed Feb. 24, 1966 now US. Pat. No. 3,451,964.

This invention relates to novel organopolysiloxane gum compositions, to processes for preparing said organopolysiloxane gum compositions; to room temperature vulcanizable compositions containing said organopolysiloxane gums; and to the elastomers prepared from said room temperature vulcanizable compositions.

Silicone elastomers based on diorganopolysiloxane polymers are well-known products and are presently enjoying an expanding market in the field of elastomers, due in part to the unusual physical properties which are obtained with these materials, physical properties which are not readily obtainable with other types of elastomers. To date two general methods have been employed for vulcanizing silicone elastomers. The older method involves the incorporation of a curing agent into a composition containing a polysiloxane gum and, if desired, other additional ingredients, and then activating the curing agent through the application of heat. Although this method is widely used in making pre-formed or molded silicone rubber products, it is inconvenient or impractical to use this method of cure in many instances where the elastomer is to be employed as a sealant, an adhesive, a caulking material and the like.

In the second method which has more recently been developed, the elastomers are cured at room temperature through the interaction of the various ingredients. During the early stages of development of this second method for preparing organopolysiloxane elastomers, it was necessary to keep one or more of the components separate from the remaining components of the curable mixture until the mixture was to be cured. This required a two-package system for preparing this type of elastomer, and it also required immediate processing and use of the gumstock after all of the ingredients of the composition had been mixed. Since the processing time (the time between the mixing of all of the various ingredients and the elastic solidfication of the productthe only time during which the mass remained plastic and workable) is generally quite short for most room temperature vulcanizable (hereinafter RTV) silicone rubber stocks, any unusued stock is usually lost; and any stock partially worked may also be lost, because it becomes difiicult or impossible to further work the stock after vulcanization has taken place. Although there have been several attempts to prolong the processing time, such as cooling the reactive mixture and/ or using solvents to dilute the reactive components, these attempts have proven to be impractical for general use. In many applications cooling cannot be achieved without the expenditure of a great deal of time, eifort or expense, and the use of solvents results in excessive shrinkage during cure. Thus, when two component systems are employed, exact planning for the processing circumstances and the quantity of material to be used in each instance is necessary, or the resulting expense of using RTV silicone rubber stocks will be unduly high, due to the resultant waste of material. The further disadvantages of the two package system of having to package, ship and store the RTV composition in at least two separate containers; and of having to mix the various ingredients just before use are apparent. The two-package system also makes it more difiicult to use small quantities of RTV silicone rubber stocks.

Several recent developments in the art of RTV elastomers have led to the development of single package RTV systems which can be packed, shipped and stored in a single container. The prime advantages of the single package systems are that they do not require the preliminary mixing of the several components just prior to use, they have indefinitely long storage life and they are immediately ready for use by simple application and exposure to the normal atmosphere in order to obtain a cure. However, all of the presently available single package systems contain as a major component a relatively high molecular weight organopolysiloxane base polymer, which necessarily results in an RTV silicone rubber composition having a relatively high viscosity prior to being cured. In many applications wherein the resulting elastomer is intended to serve as a caulk, a sealant or an adhesive in confined and/or minute areas, the relatively high initial viscosity of the RTV composition prevents or makes difficult the intimate contact necessary in order to provide a satisfactory seal.

It is an object of this invention to provide novel RTV compositions which are curable to organopolysiloxane elastomers.

It is a further object of this invention to provide organopolysiloxane elastomers which are particularly suitable for use as caulking materials, adhesives and sealants.

Other objects of this invention are disclosed in or will ble apparent from this disclosure, including the appended c am.

This invention provides a process for obtaining essentially linear, high molecular Weight organopolysiloxane gums suitable for RTV use which comprises reacting (a) a major amount of an organopolysiloxamine having the formula:

[Enem wherein R is an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, n has an average value of from about 1.8 to about 2.2, and x has an average value greater than 2, said organopolysiloxamine having an average of about two silicon-bonded amino end-blocking groups represented by the formula:

wherein R is an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, R is hydrogen, an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, or R and R together are a divalent hydrocarbon radical which forms a heterocyclic ring with the nitrogen atom to which said divalent hydrocarbon radical is attached; (b) a minor amount of an organosilicon compound having at least one silicon atom and at least three of the silicon-bonded amino end-blocking groups being defined above, each silicon atom present in said organosilicon compound being bonded to at least one of said silicon-bonded amino end-blocking groups, or to at least one other silicon atom through oxygen, the remaining valences of any silicon atoms present which are not satisfied by said silicon-bonded amino end-blocking groups, or oxygen to silicon bonds being satisfied by an unsubstituted monovalent hydrocarbon radical, a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, or a polyvalent hydrocarbon radical having each remaining free valence satisfied by a silicon atom which has its three remaining valences satisfied by unsubstituted monovalent hydrocarbon radicals, substituted monovalent hydrocarbon radicals wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, silicon-bonded amino end-blocking groups as defined above, or oxygen to silicon bonds; and (c) a minor amount of water. The organopolysiloxane gums prepared according to this process usually range in molecular weight from about 300,000 to about 5,000,000.

This invention also provides RTV compositions which comprise an acid catalyst and either (1) an organosilicon compound having at least one silicon atom and at least three of the silicon-bonded amino end-blocking groups defined above, each silicon atom present in said organosilicon compound being bonded to at least one of said silicon-bonded amino end-blocking groups, or to at least one other silicon atom through oxygen, the remaining valences of any silicon atoms present which are not satistied by said silicon-bonded amino end-blcking groups, or oxygen to silicon bonds being satisfied by an unsubstituted hydrocarbon radical, a substituted hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, or a polyvalent hydrocarbon radical having each remaining free valence satisfied by a silicon atom which has its three remaining valences satisfied by unsubstituted monovalent hydrocarbon radicals, substituted monovalent hydrocarbon radicals wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, silicon-bonded amino end-blocking groups as defined above, or oxygen to silicon bonds and an organopolysiloxamine having the formula rtnsio 4-11 wherein R is an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, n has an average value of from about 1.8 to about 2.2, and x has an average value greater than 2, said organopolysiloxamine having an average of about two silicon-bonded amino end-blocking groups represented by the formula wherein R is an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, R is hydrogen, an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups, and nitro groups, or R and R together are a divalent hydrocarbon radical which forms a heterocyclic ring with the nitrogen atom to which said divalent hydrocarbon radical is attached; or (2) an essentially linear high molecular weight organopolysiloxane gum reaction product of said organopolysiloxamine and said organosilicon compound.

This invention also provides organopolysiloxane elastomers which may be obtained by exposing of the above mentioned RTV compositions to water, such as moisture in air.

The Organopolysiloxamines which are useful in preparing the high molecular weight organopolysiloxane gums and RTV compositions of this invention are compounds having the general formula:

wherein R is an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, n has an average value of from about 1.8 to about 2.2, and x has an average value greater than 2. said organopolysiloxamine having an average of about two silicon-bonded amino end-blocking groups represented by the formula:

wherein R is an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, R is hydrogen, an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, or R and R together are a divalent hydrocarbon radical which forms a heterocyclic ring with the nitrogen atom to which said divalent hydrocarbon radical is attached. Organopolysiloxamines wherein x has a value of from about to about 200 are particularly preferred.

The above mentioned Organopolysiloxamines are essentially linear compounds, and may contain small amounts of low molecular weight cyclic siloxanes as impurities from the process used in preparing said organopolysiloxamines. Since these cyclic compounds have no organofunctional end-blocking groups present therein, the presence of small amounts of low molecular weight cyclic siloxane impurities has little elfect, if any, on the properties and reactivity of the Organopolysiloxamines, and they merely act as a diluent. The Organopolysiloxamines themselves may contain varying proportions of organosiloxane units having the general formulae:

R SiO and within the scope of the general formula for the first organopolysiloxamines which is set forth above, and the organic groups attached to each silicon atom may be the same or different. These Organopolysiloxamines are fluid polymers ranging in viscosity at 25 C. of from about 3 centipoises to about 300,000 centipoises, preferably from about centipoises to about 50,000 centipoises, and may consist of a single polymer or mixtures of two or more polymers. Minor amounts of end-blocking groups other than groups and substituted monovalent hydrocarbon groups amines, end-blocking groups such as halogens, alkoxy groups, aryloxy groups, acyloxy groups, and the like.

Illustrative of the types of monovalent hydrocarbon groups may also be present in these organopolysilox represented by R, R and R in the above-mentioned formulae are alkyl groups, such as methyl, ethyl, propyl, n-butyl, t-butyl, n-octyl, n-octadecyl, and the like; aryl groups, such as phenyl, l-naphthyl, and the like; cycloalkyl groups, such as cyclobutyl, cyclohexyl, and the like; alkaryl groups, such as p-tolyl and the like; aralkyl groups, such as benzyl, 2-phenylethyl and the like; olefinically unsaturated hydrocarbon groups, such as vinyl, allyl, 3- butenyl, 3-cyclohexenyl, ethylnyl, propynyl, 3- vinylphenyl, and the like; substituted alkyl groups such as 3- chloropropyl, Z-cyanoethyl, 3-cyanopropyl, 3-methoxypropyl, 2-ethoxyethyl, 3-aminopropyl, 4-(dimethylamine) butyl, 3-carbethoxypropyl, 3,3,3-trifluoropropyl and the like; substituted aryl groups such as p-phenoxyphenyl, 3-bromophenyl, 3,5-dibromophenyl, 3-nitrophenyl, 4- fluorophenyl, 4-cyanophenyl and the like; and substituted alkaryl groups, such as 3-trifluormethylphenyl, 3-(dimethylaminomethyl)phenyl and the like.

As hereinbefore indicated, R and R taken together can represent a divalent hydrocarbon radical which forms a heterocyclic ring with the nitrogen atom to which it is attached. For example, when R and R taken together represent a divalent hydrocarbon radical the group may represent such groups as morpholino radicals, piperidino radicals, pyrrolidino radicals and the like. Organopolysiloxamines wherein R is primarily an alkyl group, such as methyl or ethyl and wherein R and R are also alkyl groups such as methyl groups are preferred.

The above-mentioned organopolysiloxamines may be conveniently prepared in several ways, one of which involves equilibrating mixtures of organohalosilanes with organosiloxanes in the presence of an acidic catalyst to form halogen end-blocked organopolysiloxanes, subsequently reacting the halogen end-blocked organopolysiloxanes with primary or secondary amines, or mixtures thereof, in the presence of an acid acceptor, separating the acid acceptor-hydrogen halide salt by-product, and recovering the organopolysiloxamine. The resulting organopolysiloxamine can itself be hydrolyzed and condensed to form higher molecular weight polymers which may also be used in the practice of this invention. For example, the lower molecular weight organopolysiloxamines (i.e. those having a viscosity of about 5 centistokes) may readily be converted to essentially linear higher molecular weight gums merely by exposing these lower weight compositions to moist air.

The polyfunctional organosilicon compounds which are useful in preparing the organopolysiloxane gums and RTV compositions of this invention are any organosilicon compounds which have at least one silicon atom and at three of the silicon-bonded amino end-blocking groups defined above, each silicon atom present in said organosilicon compound being bonded to at least one of said silicon-bonded amino end-blocking groups, or to at least one other silicon atom through oxygen, the remaining valences of any silicon atoms present which are not satisfied by said silicon-bonded amino end-blocking groups, or oxygen to silicon bonds being satisfied by an unsubstituted monovalent hydrocarbon radical, a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, or a polyvalent hydrocarbon radical having each remaining free valence satisfied by a silicon atom which has its three remaining valences satisfied by unsubstituted monovalent hydrocarbon radicals, substituted monovalent hydrocarbon radicals wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, siliconbonded amino end-blocking groups as defined above, or oxygen to silicon bonds. The term polyfunctional organosilicon compound as such herein is meant to include those compounds immediately defined above (i.e. those which contain three or more of the silicon-bonded endblocking groups hereinbefore defined), but is not meant to include the aminosiloxy end-blocked organopolysiloxamines which were previously defined and which have an average of about 2 silicon-bonded amino end-blocking groups per molecule. These polyfunctional organosilicon compounds include organosilylamines having the general formula:

X,,Si(NR R wherein R is an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups and alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, R is hydrogen, an unsubstituted monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups, and nitro groups, or R and R together are a divalent hydrocarbon radical which forms a heterocyclic ring with the nitrogen and to which said divalent hydrocarbon radical is attached, a is 0 to 1, and X is a monovalent hydrocarbon radical, a substituted monovalent hydrocarbon radical wherein the substituents are selected from the class consisting of halogens, cyano groups, alkoxy groups, aryloxy groups, amino groups, carbalkoxy groups and nitro groups, or a group having the formula wherein w is an integer having a value of from 1 to about 10, y is an integer having a value of from 1 to about 1,000, and R and R are as hereinbefore defined, or a group having the formula:

wherein R and R are as hereinbefore defined. Homopolymeric derivatives of the above-mentioned organo silylamines which are useful in the practice of this invention are aminosiloxanes containing at least three of the required amino end-blocking groups and consisting essentially of units having the general formula:

Z,,si(NR R ).,0

wherein R and R are as hereinbefore defined, p is 0, l, 2 or 3, q is O, l, 2 or 3, the sum of p-l-q is never greater than 3, and Z is a group selected from the class consisting of R,

wherein R, R R x and y are as hereinbefore defined, c is 0,1, 2 or 3, d is 0,1, 2 or 3 and the sum of c-l-d is never greater than 3.

Copolymeric derivatives of the above-mentioned organosilylamines which are useful in the practice of this invention are aminosiloxanes containing at least three of the required amino end-blocking groups and consisting essentially of units having the general Formula I above and units of the general formula:

ReSlOil? wherein R is as hereinbefore defined, and e is 0, 1, 2 or 3.

The above-mentioned organosilylamines may be conveniently prepared in several ways, one of which involves reacting organohalosilanes with primary or secondary amines, or mixtures thereof, together with acid acceptors, separating the acid acceptor-hydrogen halide salt by products and recovering the organosilylamine. The resulting organosilylamine may then be reacted with limited amounts of water and upon removal of the evolved amine, a homopolymeric aminopolysiloxane which is also useful in the practice of this invention can be obtained; or the organosilylamine can be reacted with other functional silanes or siloxanes in the presence of water, to obtain copolymeric aminopolysiloxanes which are also useful in the practice of this invention upon removal of the byproduct of reaction between the amino group and the functional group present in the functional silane or siloxane. Organosilylamines and the homopolymeric and copolymeric derivatives of said organosilylamines wherein R is primarily an alkyl group, such as methyl or ethyl and wherein R and R are also alkyl groups such as methyl, are preferred. Illustrative of the types of polyfunctional organosilylamines and aminosiloxanes which may be employed in the practice of this invention are compounds such as CH Si[N(CH 1 and The polyfunctional organosilicon compounds are preferably employed in amounts ranging from about 001 part by weight to about 20 parts by weight per 100 parts by weight of organosiloxamine. From 0.10 part by weight to about 5 parts by weight per 100 parts by weight of organosiloxamine are particularly preferred.

The acid catalysts which are useful in preparing the RTV compositions of this invention are any of the Bronsted-Lowry acids, Lewis acids or compounds of these acids which decompose or dissociate to generate such acids in active form. These types of acids include Bronsted-Lowry protonic acids exhibiting pK values of less than 8, aprotic Lewis acids, and compounds which readily generate these acids. Illustrative of the types of acids which can be used as catalysts in the practice of this invention are the mineral acids, such as the hydrohalogen acids (e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid and the like), the oxyhalogen acids (e.g.,

iodic acid, chloric acid, perchloric acid, and the like), the oxy acids of sulfur (e.g., sulfurous acid, sulfuric acid, chloro-sulfonic acid, persulfurnic acid, and the like) oxy acids of phosphorus (e.g., orthophosphoric acid, orthophosphorus acid, hypophosphorous acid and the like), complex acids (e.g., natural acid clays, synthetic aluminas, synthetic alumino silicates), and Lewis acids (e.g., the chlorides, bromides and iodides of aluminum, boron, iron and zinc); organic acids such as the carboxylic acids (e.g., formic acid, acetic acid, cyanoacetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, trifluoroacetic acid, propionic acid, hexauoic acid, bromohexanoic acid, benzoic acid, thiobenzoic acid, oxalic acid, maleic acid, succinic acid, adipic acid, phthalic acid, citric acid, tartaric acid, acrylic acid, polyacrylic acid and the like), the sulfonic and sulfinic acids (e.g., benzene sulfonic acid, toluene sulfonic acid, benzene sulfinic acid, polystyrene sulfonic acid, and the like), and the phosphonic acids (e.g., phenyl phosphonic acid, and the like); and acid generators such as anhydrides (e.g., sulfur dioxide, sulfur trioxide, phthalic anhydride, maleic anhydride, and the like), acyl halides (e.g acetyl bromide, benzoyl chloride, carbon oxychloride, sulfuric oxychloride, thionyl chloride, thionyl bromide, phosphorous oxychloride, selenium oxychloride, and the like), halides of sulfur and phosphorous (e.g., sulfur dichloride, phosphorous trichloride, phosphorous tribromide, phosphorous pentachloride, and the like), titanium acylates and halides (e.g., titanium tetrachloride, titanium tetrabromide, diacetoxytitanate, and the like), silicon acylates and halides (e.g., silicon tetrachloride, hydrogen trichlorosilane, methyltrichlorosilane, diphenyldichlorosilane, dimethyldiacetoxysilane, phenyltriacetoxysilane and the like), ammonium and amine salts of protonic acids (e.g., ammonium sulfate, ammonium chloride, dimethylammoniumacetate, ethylmethylammonium caproate, dimethylammonium trichloroacetate, praseodymium ammonium benzoate, dimethyl ammonium chloride, and the like), and tertiary amine salts of Lewis acids (e.g., trimethylarninoboronfiuoride, dipyridine zinc chloride and the like).

The acid catalyst is preferably employed in amounts ranging from about 0.001 part by weight to about 5.0 parts by weight per parts by weight of the organopolysiloxamine. From about 0.01 part by weight to about 2.0 parts by weight of catalyst per 100 parts by weight of polysiloxamine are particularly preferred.

The amount of water employed in preparing both the organopolysiloxane gums and the elastomers of this invention is not narrowly critical, as is evidenced by the fact that both gum formation and elastomer formation occurs upon exposure of the various compositions of this invention to moist air, for example, air having a relative humidity of fifty percent at 72 F. Exposure to drier air would merely extend the period of time necessary in order to obtain a gum of a fully cured elastomer, whereas exposure to moister air would shorten the time required to obtain a gum or cured elastomer.

In addition to the above mentioned components, the RTV compositions of this invention may also contain additional components such as filler materials, coloring agents, plasticizers, softeners, odorants, thermal stabilizers, bonding additives, anti-oxidants, and the like. The fillers which may be employed in preparing the improved organopolysiloxane formulations and elastomers of this invention include the highly-reinforcing carbon black and the inorganic compounds heretofore employed as fillers in organopolysiloxane elastomers in accordance with customary procedures, and they also include finely divided, polymeric organic materials such as polyethylene, polypropylene, polystyrene, polyvinylfluoride, polytetrafluoroethylene, polyhexamethylene adipamide, polymethylene phenol, and the like. These filler materials can be employed either alone or in any suitable combination. If desired, the fillers can be treated with modifying agents,

such as the hydrolyzable hydrocarbon silanes or siloxanes, to improve their surface characteristics.

When inorganic fillers are employed in preparing the improved formulations and elastomers of this invention, it is preferable that such fillers be finely-divided, silicabase materials having a particle diameter of less than 500 millimicrons and a surface area of greater than 50 square meters per gram. However, inorganic filler materials having a composition, or particle diameter and surface area, other than those preferred can also be employed alone or in combination with the preferred fillers. Thus, such filler materials as titania, iron oxide, aluminum oxide, aluminum silicate, zinc oxide, zirconium silicate, diatomaceous earth, and quartz can be employed either alone or in combination with the finely-divided, silica-base fillers described above.

The amount of highly-reinforced silica employed as filler in preparing the improved formulations and elastomers of this invention depends upon the tensile strength and hardness properties desired in the elastomer. By way of illustration, where high tensile strength and high hardness properties are required, large amounts of highlyreinforcing silica are employed, together with smaller amounts of other type fillers, if such be desired. Where high tensile strength and high hardness properties are not as important, for example, when the elastomers are to be employed as coatings or cable compounds, lesser amounts of highly-reinforcing silica can be employed together with the larger amounts of other types of fillers.

The compositions of this invention are prepared by mechanically mixing together the various components which are to be included in the desired composition. The particular design of the mixing equipment and the method and order of the various components is not critical, although there are some preferred conditions under which the mixing of the various components should be conducted. For example, since the compositions are reactive in the presence of water, it is essential that the mixing of the various components is conducted under anhydrous or nearly anhydrous conditions. Hence, enclosing the mixing equipment so that the ambient atmosphere can be controlled is preferred. Also, since the compositions of this invention which do not contain an acid catalyst are mildly basic in nature, it is desirable to exclude or control their contact with any acidic or potentially acidic environmental components such as S CO or HCl which may be found in the atmosphere. In some cases it may be desirable to add during the preparation of the compositions of this invention very small, controlled amounts of water in order to adjust the viscosity of the resulting composition. It also may be desirable to dry or dehydrate any additional components which are to be added, such as filler materials which often contain adsorbed moisture, prior to the incorporation of these components into the compositions of this invention; or these additional components might be incorporated into the compositions of this invention after the other components have been admixed.

As hereinbefore indicated, the compositions of this invention behave in either of two different ways upon exposure to water, such as moisture in the air, depending on the presence or absence of an acid catalyst. In the case of those compositions which contain only an organopolysiloxamine and a polyfunctional organosilicon compound of the type hereinbefore described, and no acid catalyst, the compositions undergo a reaction to form an essentially linear, soluble, high molecular weight organopolysiloxane gum. In the case of those compositions which contain either the above-mentioned organopolysiloxamine, a polyfunctional organosilicon compound of the type hereinbefore described and an acid catalyst, the composition undergoes a reaction to form an insoluble elastomer. Although the reactions involved in each instance are not known for certain and are difiicult to ascertain, it appears that in the first instance (i.e., the

reaction involving only the organopolysiloxamine and the polyfunctional organosilicon compound to form a high molecular weight gum, the polyfunctional organosilicon compound merely acts as a chain extender by reacting with the terminal aminosiloxy units which are present in the organopolysiloxamine. Since the resulting high molecular weight organopolysiloxane gum remains soluble in solvents such as hexane, it would appear that surprisingly little or no crosslinking has occurred. In prior art systems which employ linear polymers end-blocked with other types of functional groups, either no gum formation occurs upon exposure to moisture at ambient temperature in the absence of a catalyst, or gum formation occurs very slowly over a prolonged period of time, such as several weeks. In the second instance (i.e. the reaction, involving either the high molecular weight organopolysiloxane gum product and the acid catalyst, or the organopolysiloxamine, the polyfunctional organosilicon compound and the acid catalyst), it appears that the acid catalyst catalyzes a cross-linking reaction between (a) either the residual aminosiloxy groups present in the organopolysiloxane gum or the aminosiloxy groups of the organopolysiloxamine, and (b) the amino groups of the polyfunctional organosilicon compound, whereas one might expect the amino compounds to neutralize or form a salt with the acid present.

The RTV compositions of this invention are useful in the same areas as conventional silicone rubber RTV compositions (e.g., as sealants, caulks, coatings and adhesives), and they are also useful in preparing casting molds, replicas and dental impressions.

The following examples are illustrative of this invention. The terms and expressions employed in the examples and throughout this specification are to be interpreted as indicated in the glossary immediately preceding the examples.

GLOSSARY (A) Hardness (ASTM D-676-49T) Degree of indentation produced by a plunger of indentor under a specific load. Measured with a Shore A Durometer. The values range from 0 to a maximum hardness of 100.

(B) Tensile strength (ASTM D-4l2-49T) The force necessary to rupture specimen when stretched to the breaking point divided by the original cross sectional area (pounds per square inch) a (C) Elongation (ASTM D-412-51T) Amount of stretch of a sample under a tensile force expressed as a percentage of the original length.

(Stretched length minus original length) x 100 original length EXAMPLE 1 grams of a polymer of the formula:

having a viscosity of 650 centistokes were mixed with 1 gram (equivalent to approximately 2 parts by weight per parts by weight of the organopolysiloxamine) of hour period, a gum-like polymeric product was obtained which was completely soluble in n-hexane.

1 1 EXAMPLE 2 50 grams of a polymer of the formula having a viscosity of 650 centistokes were mixed with 1 gram (equivalent to approximately 2 parts by weight per 100 parts by weight of the organopolysiloxamine) of CH Si[N(CH Three drops of glacial acetic acid (equivalent to approximately 0.36 part by weight of the organopolysiloxamine) were added to 15 grams of this mixture, and the resulting liquid was poured into a petri dish and exposed to 50% relative humidity at 72i2 F. Within minutes a cross-linked elastomeric product was obtained which was insoluble in n-hexane.

EXAMPLE 3 100 grams of a fluid of the formula:

containing approximately 1.07% by weight of dimethylamino groups attached to silicon were mixed with 1 gram of CH Si[N(CH 18 grams of diatomaceous earth (Celite), and 42 grams of ground quartz (Minusil). About 60 grams of this mixture were poured into a mold 6 inches by 6 inches by of an inch, and 4 drops (equivalent to approximately 0.4 part by weight per 100 parts by weight of the organopolysiloxamine of an organic acid (Sarcosyl LC) having the formula CH3(CH2) C 0 NCH2C CH3 OH (wherein 11:12 to 18) were added to the remainder of the mixture before pouring this material into a mold also. Both samples were then exposed to 50% relative humidity at 72:2 F. The first portion of the above-mentioned mixture, that portion which did not contain any acid, resulted in a filled gumstock after standing for two weeks. This composition appeared to have little of any crosslinks and did not exhibit the properties of an elastomer. The second portion of the above-mentioned mixture, that portion which contained the acid catalyst, resulted in an elastomer having the following properties after 24 hours of exposure.

Hardness (Shore A) 37 Tensile (p.s.i.) 850 Elongation (percent) 315 EXAMPLE 4 100 grams of a polymer having the formula:

containing approximately 1.07% by Weight of dimethylamino groups attached to silicon were mixed with 2 grams of CH Si[N(CH drops (equivalent to approximately 0.6 part by weight per 100 parts by weight of the organopolysiloxamine) of 2-ethylhexanoic acid and 40 grams of finely divided polyvinylchloride in a dry nitrogen atmosphere. This composition was sealed in metal dispensing tubes and stored for a three month period. At the end of this storage period, a sample of the composition was exposed to an atmosphere of 50% relative humidity at room temperature; and, upon standing overnight in this atmosphere, the composition cured to a useful elastomer.

12 EXAMPLE 5 wherein 11:12 to 18 (equivalent approximately to 0.12 part by weight per parts by weight of organopolysiloxamine). A portion of this composition was poured into an aluminum dish and exposed to atmospheric moisture. Within minutes, a cross-linked elastomer was formed which strongly adhered to the aluminum dish. The adhesion was such that it was impossible to remove the cured elastomer from the container without rupture of the rubber at the cured rubber-aluminum interface.

EXAMPLE 6 10 grams of a polymer of the formula:

CH3 CH3 (CHa)2N[S iO S iN(CHs)z n-13 (3113 containing approximately 1.09% by weight of dimethylamino groups attached to silicon and having a viscosity of 580 centistokes were mixed with 0.14 gram of (equivalent to 1.4 parts by weight per 100 parts by weight of organopolysiloxamine). The resulting mixture was divided into two equal portions, one of which was sealed, and one of which was exposed in a thin film to the atmosphere. There was no change in the sealed portion, whereas the exposed portion formed a soluble gum upon standing overnight.

EXAMPLE 7 10 grams of a polymer of the formula:

containing approximately 1.09% by weight of dimethylamino groups attached to silicon and having a viscosity of 580 centistokes were mixed with 0.05 gram of CH Si[N(CH (equivalent to 0.5 part by weight per 100 parts by weight of organopolysiloxamine) and 0.16 gram of diacetoxydimethylsilane (equivalent to 1.6 parts by weight per 100 parts by weight of organopolysiloxamine). The resulting mixture was divided into two equal portions, one of which was sealed, and one of which was exposed in a thin film to the atmosphere. There was no change in the sealed portion, whereas the exposed portion exhibited noticeable cross-linking within 5 minutes after being exposed.

EXAMPLE 8 100 grains of a polymer of the formula:

CH3 CH2;

having a viscosity of 500 centistokes were mixed in a vertical Atlantic Research mixer with 1.5 grams of bis- [tri(dimethylamino)silyl]ethane, 0.1 gram of an organic acid (Sa-rcosyl LC) having the formula:

0 Ha 0 H2) nC IIL-CHzO OHa OH (wherein 11:12 to 18) and 25 grams of a precipitated silica filler which had previously been treated with 15 parts by weight per 100 parts by weight of silica of a dimethylsilicone oil (Quso M-SO). Approximately 60 grams of this mixture were placed in a standard ASTM rubber testing slab and exposed to an atmosphere of 50% relative humidity at room temperature (72 F.). After fifteen minutes the sample was tack-free, and upon standing overnight in this atmosphere the composition cured to a useful elastomer exhibiting the following physical properties:

Tensile strength (p.s.i.) 600 Elongation (percent) 250 Hardness (Shore A) In order to test the bonding properties of the elastomer obtained from this mixture, portions of the mixture were placed on cloth, glass, steel, and stainless steel specimens and exposed overnight to an atmosphere of relative humidity at 72 P. On the following day, the elastomer could not be removed from the cloth, glass and steel specimens Without rupture of the rubber at the cured elastomer-specimen interface. Although the elastorner was removed from the stainless steel specimen without rupture of the elastomer, excellent adhesion also was observed and it was quite difficult to peel the elastomer off the surface of the specimen.

What is claimed is:

1. An organosilicon compound having the formula References Cited UNITED STATES PATENTS 3,297,592 1/1967 Fink 260-4482 X 3,417,115 12/1968 Stamm 260448.2 X 3,445,426 5/1969 Lee 260448.2 X 3,445,492 5/ 1969' Washburn et al. a, 260-448.2 X

TOBIAS E. LEVOW, Primary Examiner W. F. W. BELLAMY, Assistant Examiner US. Cl. X.R. 

